DE1290645B - Process for the preparation of strongly basic alkaline earth alkylthiophenolates - Google Patents

Description

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In the patent application C 29 934 IVc / 23 c the addition of the metal oxide or hydroxide takes place

(German Auslegeschrift 1278 053) is a ver so that in the first stage about 50 to 85 weight

process for the production of oil-soluble, strongly basic percent, based on the total amount added,

carbonized alkaline earth alkylthiophenolates are described.

ben, the metal content of which is more than 20% above that of the 5 Percentage of the alkylphenol used in the invention. According to the method according to the invention, the percentage content of the "normal" phenolates contained in "normal" phenolates is first produced in a mixture which is 1.2 to 4.5 or more from an alkyltenene metal. phenol, a sulfonate, an alcohol with a high molecular weight, an oil with lubricating viscosity IVc / 23c, consists in that one consists of alkylphenolates with and sulfur. This mixture is then converted to alkaline earth oxides or hydroxides and heated to temperatures in the range from 121 to 149 ° C, then with CO ₂ in the presence of glycol, 15 At this temperature, hydrated lime is then basic sulfonates and a monohydric alcohol with stirring and then added glycol. That carbonizes with high molecular weight. After the addition of the glycol, it is essential that the reaction mixture contains (1) a water is then removed by distillation, and sulphonate, (2) a glycol and (3) an alcohol with subsequent carbonation by means of a high molecular weight, and that in the αο carbon dioxide at temperatures of 121 to 163 ° C. finished basic phenolate-oil mixture still sulfonate. All of the unbound CO ₂ is then removed and part of the alcohol is contained. The second addition of the hydrating lime has now been found that even better results are then carried out at the same temperatures if the addition of the earth is followed by the removal of water of reaction and then alkali oxide or hydroxide in two separate stages making further addition of carbon dioxide for the second. The present invention therefore relates to carbonization at temperatures between a process for the production of basic Erd- 121 and 163 ° C. The reaction mixture is then alkali alkylthiophenolates in lubricating oils by heating a mixture of a lubricating oil, a mixture of a lubricating oil, for 2 to 10 hours at temperatures of 150 to zen 200 ° C, and the absolute pressure is reduced to 40 to 50 Torr during alkylphenol with 4 to 30 carbon atoms in the 30th of this heating. Alkyl radical, an alkaline earth sulfonate, a monovalent ethylene glycol escapes. In certain cases alcohol with 8 to 18 carbon atoms, further some of the alcohols with high molecular heating with addition of sulfur, an alkaline earth weight together with the ethylene glycol removes metal hydroxide or oxide and ethylene glycol. However, regardless of whether the alcohol is removed from the water of reaction, the introduction of carbon with the high molecular weight not at all, dioxide and the distillation of ethylene glycol is partially or completely removed, the de-stemming pressure according to patent application C 29 934 is the lubricating oil preparation for the intended IVc / 23 c (German Auslegeschrift 1278 053), which. Purpose of use well suited. When using the method is characterized in that one particularly preferred alcohol with a high next to the mixture of lubricating oil, alkylphenol, 40 molecular weight, ie tridecyl alcohol, it is favorable, alkaline earth metal sulfonate, the alcohol and sulfur, one that at least 50 percent by weight in the lubricating oil - Part of the alkaline earth oxide or hydroxide remain prepared together. The finished lubricating oil preparation with the ethylene glycol is added, but then after removal it can also contain 30 to 50 percent by weight or up of the water of reaction and after introducing CO ₂ to 100%, based on the originally used again the remaining part of the alkaline earth metal salts to 45 tridecyl alcohol, sets, whereupon the mixture is treated further. As

in the process of patent application C 29 934 Example I

is a mixture of an alkylphenol, a -.

High molecular weight alcohol, lubricating oil, and basic carbonated manufacture

Sulfur produced and heated with stirring. Im ₅₀ calcium alkenyl thiophenolate

In contrast to the process described there, a mixture of 3976.5 1 of an alkylphenol is used

however then the hydrogenated lime (or CaO) in two 65 ° C, wherein the alkyl radical of a polypropylene

added to separate stages. After the first addition with an average of 12 carbon atoms,

From hydrated lime, ethylene glycol is added to a refined Californian base oil

give and the water of reaction removed; then 55 at 38 ° C, with viscosities of 130 SSU at 38 ° C,

Carbon dioxide is added and unbound CO _{2 is} obtained from a basic calcium sulfonate 400.61 at 38 ° C,

far away. This is followed by the second addition of hydrati- which 40% more calcium than a neutral sulfonate

Calcified lime, the removal of water of reaction, contains (i.e. the base ratio was 1.4: 1), 384 kg

the further addition of carbon dioxide and the ent- tridecyl alcohol and 750 kg of sulfur were in one

removal of glycol and alcohol. 60 kettle introduced and with stirring to 127 ° C

The high molecular weight alcohols that are heated. The first part of hydrated lime,

in amounts not greater than 15 percent by weight, 1263 kg, was added to the mixture at 127 ° C,

preferably 5 to 12%, based on the consumption. The reaction mixture was at 45 cm vacuum

used alkylphenol, are heated to 138 ° C, and there were 215 liters of ethylene glycol

valued alcohols with 8 to 18 carbon atoms. 65 added.

Examples include octyl alcohol, decyl alcohol, the glycol was slow at a temperature

Dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, added from 132.2 to 137.8 ° C. After that, that became

Cetyl alcohol. The reaction mixture was heated to 149 ° C. and left

increase the vacuum to 55 cm; the reaction kettle was held under these conditions for 1 hour.

With rapid stirring of the reaction mixture, 504 kg of CO _{2 were added} at an initial rate of 90.6 kg / hour. was added and this rate was increased to 226 kg / hr. gradually increased. During the _{addition of CO 2} , the boiler pressure did not rise above 2.1 kg / cm ² . The temperature was maintained between 146 and 154 ° C. Any excess pressure was released and a vacuum was applied to remove _{unbound CO 2.}

The second part of the hydrated lime, namely 504 kg, was then introduced into the reaction kettle at a temperature between 127 and 143 ° C. The temperature was held at 149 ° C. for 2 hours under a vacuum of 55 cm. The second addition of 199 kg of CO ₂ was then carried out at 146 to 154 ° C. at a rate of 90.6 to 113 kg / hour. The temperature of the reaction kettle was then increased to 200 ° C with a vacuum of at least 70 cm to remove the glycol and no more than 70 weight percent of the original charge of the tridecyl alcohol over a period of 1 hour (under final conditions).

Example II

Production of basic, carbonized
Alkyl thiophenolate

A mixture of 6480 g (20 mol) of an alkyl phenolate, wherein the alkyl radical of a polypropylene having an average of 12 carbon atoms 5184 grams of a solvent refined Californian oil having a viscosity of 150 SSU at 38 ° C, 648 g of tridecyl alcohol, 648 g of a basic calcium sulfonate and 1260 g (39.3 mol) Sulfur was introduced into a 37.8 liter reaction kettle heated to 93 ° C. The mixture was stirred thoroughly, and the first addition of hydrated lime was in an amount of 2120 g (28.6 moles). The temperature rose rapidly to 149 ° C, and at the same time the pressure decreased decreased to 200 torr. At the temperature of 149 ° C were 4040 g of ethylene glycol (65 mol) during added over a period of 30 minutes, then the reaction mixture was heated to 149 ° C and 200 torr held for about 1.5 hours.

For the first carbonation stage, 834 g of CO ₂ (19 mol) were added at a temperature of 149 ° C. over a period of 1 hour at atmospheric pressure. The reaction mixture was kept at 149 ° C. and the pressure was reduced to 200 torr in order to remove the water of _{reaction and the unreacted CO 2.}

The second addition of hydrated lime was then made in an amount of 846 g (11.4 moles) at 149 ° C. Water was removed by distillation, followed by a second carbonation stage with 334 g CO ₂ (0.76 moles) at 149 ° C ° C for 8 minutes.

The reaction mixture was then at a pressure of 20 torr for a time of Heated to 204 ° C. for 3.5 hours and then filtered. The reaction product contained 9.2 percent by weight Calcium, which is about 29 moles more than the amount contained in the neutral calcium phenate.

ίο In the above embodiment of the invention In the process, the basic substances and the carbon dioxide are added in two portions. The amount of metal present in the phenolates can be determined by adding more basic substances Increase substances and carbon dioxide.

As mentioned above, the finished lubricating oil preparation should have a high base value. In the method described, the starting amount of alkylphenol should be 20 to 40 percent by weight,

ao based on the finished preparation, preferably 30 to 40 percent by weight. The lubricating oil reaction medium is used in amounts of 15 to 50 percent by weight, based on the finished preparation, preferably 20 to 30 percent by weight used.

The metal sulfonate used in the above examples was a concentrate consisting of 46.4 percent by weight of a mineral lubricating oil and 53.6 percent by weight of a calcium petroleum sulfonate existed, with the petroleum residue from a mineral oil with a viscosity of 500 SSU 38 ° C. The calcium content of the oil concentrate was 2.35 percent by weight and the base ratio was 1.4.

Claims (1)

Claim: Process for the preparation of basic alkaline earth alkylthiophenolates in lubricating oils by heating a mixture of a lubricating oil, an alkylphenol with 4 to 30 carbon atoms in the alkyl radical, an alkaline earth sulfonate, a monohydric alcohol with 8 to 18 carbon atoms, further heating with addition of sulfur, an alkaline earth metal hydroxide or oxide and ethylene glycol, removing the water of reaction, introducing carbon dioxide and distilling off ethylene glycol at reduced pressure according to patent application C 29 934 IVc / 23 c (German Auslegeschrift 1278 053), characterized in that first the mixture of lubricating oil, alkylphenol, alkaline earth metal sulfonate, the alcohol and sulfur, a part of the alkaline earth metal oxide or hydroxide together with the ethylene glycol, then, after removing the water of reaction and after passing in CO _2, again adding the remaining part of the alkaline earth metal salts, whereupon the mixture is treated further.